Azo dyestuffs derived from amino-acylamino-salicyl-diphenylsulfones



Patented Apr. 28, 1931 UNITED gsrnrrzsv WILHELM NEELMEIER, ,onLvERKUsEN, NEAR .Loo'LoeNn onernngnnmn, AND rnrn'rrnnrnrcrr, or wrnsnonr,NEAR oor oennformrrm-nrrmnaglimmer ssrenons T0 GENERAL AnIL rNEwonKs,and; ornnw renn n. 1., n conro nnarron or DELAWARE AZO :oynsrorrsDERIVED FROM AMINO-.ACYL-ufillffili!) fSgAgLiCQfLfDIIPEEIQLSULFQNES I'lvo llrawi ng Applie' ation filedllilay25, 1927, Serial No. 194,229, ang 1 im-Germany January -13, 4325. 1

This intention-relates to -raluable mordant dyestuffs whichcontain-residues of such amino-derivativesof diphenylsulfones,

their homologs or substitution products, as

have, in the nucleus which does not contain the amino group, an hydroxylgroup and a carboxyl group in ortho position to each other. i I

In-our co;pending application ,Serial No. 146,558, filed Nov. '5, 1926we have described wdye ltufi e e ra afQ mlilfii wherein R representshydrogen-1gor an ,acid'yl group, represents a-residue offa -couplingcompound, and the hydroxyl group-aridthe carboxyl group stand in orthoposition to eachother; which dyestuffs may he obtained by couplinganydesired coupling component with the diazo-compoundsofidiaminophenylsalicyl sulfones having the general formula:

eini epre ent hydr e e i group, and;t he hydroxyl, group "and thefcarbox yl group stand in orthoj position to each other. I 1 Q Wehave nowfoundthat similar, improved dyestuffs are obtainable by diazotiz'ing acompound of the generalyf orinula r i 7 :OH S02 wherein R and R standforalkyl or aralkyl ;and coupling the diazo {compound vthus obtainedwithfacoup'ling component;

The new dyestuffs agthus obtainable correspend with the, generalformula: V

wherein R and R represent alkyl or aralkyl v iolet shades of excellentfastness properties to soaping and-t0 fulling. 1 The same shades areobtained when wool dyed with the ,said dyestufls is" subjected jyto :anafterehroming treatment; The-dyestufis also are-suitahle 'for use: incotton iprinting, due I to their fastness 7 properties. Due to the-external position of the: groupproducing the mordant'ing proper ties,these 'dyestulfs'possess the "additional advantage thatltheir dyeingswith 'chroming vary" in shade little if :at allffrom the direct dyeings;I r As coupling compounds there maybe used any of the 'well knownazodyestufi's coupling components, but: wehave found-that veryaval uabledyestufi's areobtainedzby thense'as coupling compounds of -zaniinonaphthalene sul'fonic acids or v-a-mino-naphthol sulfonic acids.

- Our invention isjllustrated by the-followingexample: V 1 i 336partsbyweight'of 2-amin0i-5-dimethyl amino-4 ,hydroxy diphenylsulfon 3carboxylic acid, are suspended in water at .abQ t 50? C. andcaustic-soda ,solution :iswadded in quantity sufi'icient to dissolve,the compound. When the..compound isv dissolved (the solution is. Sfirglly acidified .with 120%: hydrochloric 7 1; 0 readily solublejin waterandinsulfumc acid, is

dyeing chrome mordanted wool-red to blue to 7 acid and a solution of 69parts by weight of sodium nitrite are slowly added while maintaining thesolution at 0 C. and well, stirred. The diazo compound forms as ayellowish precipitate, is separated by filtration under suction and iscoupled at ordinary temperature with'239 parts by Weight of 2-aminoi andnot sensitive .to metals.

7 The dyestuff has, in the form of its free8-hydroXy-naphthalene-6-sulfonic acid in the form of a finely dividedsuspension in glacial acetic acid containingsodiumacetate. The couplingtakes place with the production of aiviolet colorationand when it iscomplete the dyestuff is separated from the acetic acid r andtransformed in the usual manner into the sodium orammonium salt. a The,dry product is a dark powder with a violet'color, readily soluble inwater. It is soluble in strong sulfuric acid with a yellowish'tinged redcolor.

The new dyestuff gives upon wool in an acid bath a beautifulviolet-color which by-aftertreatment with chromium fluoride gives aviolet colored dyeing which is-fast to fulling and carbonizing. Thedyeing is fast to light acid, most probably the formula NT a I:

no 4! -;hydroxy diphenylsulfon -3- carboxylic acid, the corresponding diethyla'mino com- 1 pound 1s used, a similar dyestuff is obtained.

The use of:2-methylamino-8-hydroxynaphafter-treatment with wh ch doesnotsubstantially alter their color,

'thalene-(i-sulfonic acid as a coupling component gives dyestuffswhichdye Wool a red dish tinged blue color and thefdyeingsvby chromiumfluoride,

' have the fastness properties referred to above.

By heating. the water solution of the dyestuff W1l3l1' chromatingagents, for instance, chromiurn fluoride, in. the presence of an acidbin dingagent; complex chromium compounds of V thedyestufl' are formed;Thechromium CODja pounds of the dyestuff obtained from 2-1min o5-dimethylamino-t-hydroxydiphenylsulfon- 3'-carboxylic acid and- 2amiiio-8-hydroxy: naphthalene-6-sulfonic acid dye-s wool cfrom asulfuric acid bath a, fast violet color. By

-- coupling the diazo'compound of 2-amino-5 di-ethylaminoi-hyd'roxy 7diphenyl sulfon- 3v-carboxylic acid in acetic acid in thepresence ofsodium acetate with LS-dihydroXynaphthalene?3.6-disulfonic acidaYdyestuff is produced which dyes wool from 2 a id ath being a darkviolet powder, readily soluble in water, dyeing wool from an acid bathviolet shades which after chroming' are fast to fulling and carbonizing.

2. As new productsvthe mordant dyestuffs of the general formula:

10o mordanted wool red to blue to violet shades g A I g I M 'ofexcellent fastness properties to soaping If, instead .of'the2-amino-5-dimethylamicoon IRE X1 wherein R and R represent alkyl and Rstands for the residue of, a coupling component of the naphthaleneseries, said dyestuffs being'generally dark powders, readily soluble inwater and in sulfuric acid, dyeing chrome mordanted wool red to blue toviolet shades, of excellent fastness properties to soaping andtofulling. i v In testimony whereof, we afiix our signatures. v

WILHELM NEELMEIER. WINFRID HENTRICH.

Certificate of Correction Patent No. 1,803,202. Granted April 28, 1931,to

VVILHELM NEELMEIER AND VVINFRID HENTRICH It is hereby certified thaterror appears in the printed specification of the abovenumbered patentrequiring correction as follows: Page 2, lines 27 to 37 and 72 to 80,claim 1, strike out the formula and ins rt the following:

l NHg 4010-011 & mom OOH and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Oflice.

Signed and sealed this 21st day of July, A. D. 1931.

[SEAL] M. J. MOORE, Acting Commissioner 0 f Patents.

